EP2243818B1

EP2243818B1 - Use of a refrigerant and lubricating oil composition

Info

Publication number: EP2243818B1
Application number: EP09709827.1A
Authority: EP
Inventors: Masato Kaneko; Harutomo Ikeda; Tokue Sato
Original assignee: Idemitsu Kosan Co Ltd
Current assignee: Idemitsu Kosan Co Ltd
Priority date: 2008-02-15
Filing date: 2009-02-03
Publication date: 2016-02-03
Anticipated expiration: 2029-02-03
Also published as: WO2009101872A1; KR20100120145A; US20110057146A1; CN101945979B; TW200951212A; JP5241262B2; US8449789B2; EP2243818A1; KR101497179B1; TWI456047B; EP2243818A4; CN101945979A; JP2009191211A

Description

Technical Field

The present invention relates to the use of a lubricating oil composition and a refrigerant, more particularly the use of these components in a refrigerator. The refrigerant has a low global warming potential. The lubricating oil composition comprises a polyvinyl ether derivative, and the lubricating oil composition has excellent stability and suppresses the generation of sludge in a sealed tube test.

Background Art

In general, a compression-type refrigerator includes at least a compressor, a condenser, an expansion mechanism (such as an expansion valve), an evaporator, and an optional drying apparatus, and a liquid mixture of refrigerant and lubricating oil (refrigerator oil) circulates in a closed system of the refrigerator. In such a refrigerator, generally, the compressor is operated at high temperature, while the cooler is operated at low temperature, although the difference in temperature varies depending on the type of the refrigerator. Therefore, a refrigerant and a lubricating oil must circulate in the system without causing phase separation within a wide temperature range of high to low temperature. Generally, a mixture of refrigerant and lubricating oil has a phase separating region in a low-temperature range and in a high-temperature range. The highest phase separation temperature in the low-temperature range is preferably -10°C or lower, particularly preferably -20°C or lower, whereas the lowest phase separation temperature in the high-temperature range is preferably 30°C or higher, particularly preferably 40°C or higher. When phase separation occurs during operation of a refrigerator, the service life and efficiency of the refrigerator are considerably impaired. For example, when phase separation between refrigerant and lubricating oil occurs in a compressor, lubrication of a movable member is impaired, thereby causing seizure or a similar phenomenon, resulting in considerable shortening of the service life of the refrigerator. When phase separation occurs in an evaporator, a viscous lubricant remains, thereby lowering heat exchange efficiency.
A chlorofluorocarbon (CFC), a hydrochlorofluorocarbon (HCFC), or the like has been heretofore mainly used as a refrigerant for a refrigerator. However, such compounds each contain chlorine that is responsible for environmental issues, so investigation has been conducted on a chlorine-free alternative refrigerant such as a hydrofluorocarbon (HFC). A hydrofluorocarbon typified by, for example, 1,1,1,2-tetrafluoroethane, difluoromethane, pentafluoroethane, or 1,1,1-trifluoroethane (hereinafter referred to as "R134a", "R32", "R125", or "R143a", respectively) has been attracting attention, and, for example, R134a has been used in a car air conditioner system.
However, because the influence of the HFC is also concerned from the viewpoint of the global warming, so-called natural refrigerants such as carbon dioxide have attracted attention as alternative refrigerants suitable for environmental protection. The carbon dioxide requires high pressure, and hence cannot be used in the current car air conditioner system.
A refrigerant having a specific polar structure in the molecules such as an unsaturated fluorinated hydrocarbon compound (see, for example, Patent Document 1), a fluorinated ether compound (see, for example, Patent Document 2), a fluorinated alcohol compound, or a fluorinated ketone compound has been found to be a refrigerant which has a low global warming potential and can be used in a current car air conditioner system.
The lubricating oil for a refrigerator that uses the refrigerant is demanded to have excellent compatibility with the refrigerant and stability.

Patent Document 1: 2006-503961 A
Patent Document 2: JP 07-507342 A WO2005/103188 discloses blends of fluorinated propene refrigerant and lubricant base oils in refrigeration systems.

Disclosure of the Invention

Problems to be solved by the Invention

Under the circumstances, an object of the present invention is to provide a lubricating oil composition for use in a refrigerator together with a refrigerant having a specific structure, the refrigerant having a low global warming potential and being applicable to, in particular, current car air conditioner systems or the like. The lubricating oil composition has excellent stability as well as excellent compatibility with the refrigerant.

Means for solving the Problems

The inventors of the present invention have studied extensively to achieve the above object. As a result, the inventors found that the object could be achieved using a base oil consisting of a polyvinylether derivative having a hydroxyl value equal to or less than a certain value, and preferably using a specific material for a sliding part in a refrigerator. The present invention has been completed based on those findings.
An aspect of the present invention is the use of the following refrigerant (i) and lubricating oil composition (ii) in a refrigerator:

(i) a refrigerant including:
- at least one fluorinated propene, and
- optionally up to 30 mass%, based on the total mass of the refrigerant, of one or more saturated fluorinated hydrocarbon compounds; and
(ii) a lubricating oil composition comprising a base oil which consists of at least one polyvinyl ether derivative having a hydroxyl value of 17 mgKOH/g or less.

Another aspect of the invention is the use of the refrigerant and lubricating oil composition defined above in an air conditioner, preferably a car air conditioner or an electrically-driven air conditioner; a gas heat pump; a cold storage device; a hot-water supply system for a vending machine or a showcase; or a refrigerating and heating system.
Preferred aspects of the invention are defined in the dependent claims.

Effects of the Invention

The refrigerant employed in the present invention has a low global warming potential and is applicable to, in particular, current car air conditioner systems or the like. The lubricating oil composition has excellent stability as well as excellent compatibility with the refrigerant and suppresses the generation of sludge in a sealed tube test.

Best Mode for carrying out the Invention

Examples of the fluorinated propene include various kinds of isomers of pentafluoropropene, 3,3,3-trifluoropropene, and 2,3,3,3-tetrafluoropropene, and 1,2,3,3,3-pentafluoropropene (HFC1225ye) and 2,3,3,3-tetrafluoropropene (HFC1234yf) are particularly suitable.
In the present invention, one kind of fluorinated propene may be used alone or two or more kinds thereof may be used in combination.
In addition, a combination of a saturated fluorinated hydrocarbon compound having 1 to 3 carbon atoms and a fluorinated propene may be used.
Examples of the saturated fluorinated hydrocarbon compound having 1 to 3 carbon atoms include R32, R125, R134a, R134b, R152a, and R245fa. Of those, R32, R134a, and R152a are suitable. In the present invention, one kind of the saturated fluorinated hydrocarbon compound may be used alone or two or more kinds thereof may be used in combination.
Examples of the combination of the saturated fluorinated hydrocarbon compound having 1 to 3 carbon atoms and the fluorinated propene include a combination of CH₂F₂ (HFC32) and HFC1225ye, a combination of CHF₂CH₃ (HFC152a) and HFC1225ye, and a combination of CF₃I and the HFC1234yf.

[Saturated fluorinated hydrocarbon compound]

More generally, the saturated fluorinated hydrocarbon compound is a refrigerant that can be mixed, as required, with at least one kind of fluorinated propene.
As the saturated fluorinated hydrocarbon compound, a fluorinated compound of alkane having 1 to 4 carbon atoms is preferable, and fluorinated compounds of methane or ethane having 1 to 2 carbon atoms such as trifluoromethane, difluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, and 1,1,1,2,2-pentafluoroethane are particularly suitable. In addition, as the saturated fluorinated hydrocarbon compound, the fluorinated alkane may be halogenated with a halogen atom other than fluorine, and trifluoroiodomethane (CF₃I) and the like are exemplified. One kind of the saturated fluorinated hydrocarbon compound may be used alone or two or more kinds thereof may be used in combination.
The blending amount of the saturated fluorinated hydrocarbon compound is 30 mass% or less, preferably 20 mass% or less, and more preferably 10 mass% or less based on the total amount of the refrigerant.
The lubricating oil composition (hereinafter may be referred to as refrigerator oil composition) comprises a base oil which consist of at least one polyvinylether derivative having a hydroxyl value of 17 mgKOH/g or less.

[Base oil]

When the polyvinyl ether derivative has a hydroxyl value of 17 mgKOH/g or less, the stability of the refrigerator oil composition is improved and the generation of sludge is suppressed in a sealed tube test. The hydroxyl value of the polyvinyl ether derivative is preferably 15 mgKOH/g or less and more preferably 10 mgKOH/g or less.
The at least one polyvinyl ether derivative preferably contains, as a main component, a polyvinyl-based compound having a constitutional unit represented by the following general formula (I).
In the general formula (I), R¹, R², and R³ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms and may be identical to or different from one another.
The hydrocarbon group herein specifically refers to: alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups; cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, various methyl cyclohexyl groups, various ethyl cyclohexyl groups, and various dimethyl cyclohexyl groups; aryl groups such as a phenyl group, various methyl phenyl groups, various ethyl phenyl groups, and various dimethyl phenyl groups; and aryl alkyl groups such as a benzyl group, various phenyl ethyl groups, and various methyl benzyl groups. It should be noted that those R¹, R², and R³ each particularly preferably represent a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms.
On the other hand, R⁴ in the general formula (I) represent a divalent hydrocarbon group having 2 to 10 carbon atoms. Specific examples of the divalent hydrocarbon group having 2 to 10 carbon atoms herein include: a divalent aliphatic group such as an ethylene group, a phenyl ethylene group, a 1, 2-propylene group, a 2-phenyl-1,2-propylene group, a 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, and various decylene groups; alicyclic groups in which alicyclic hydrocarbon, such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and propylcyclohexane, has two bonding sites; divalent aromatic hydrocarbon groups such as various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, and various naphthylenes; alkyl aromatic groups having monovalent bonding sites in each of the alkyl group portion and the aromatic portion of the alkyl aromatic hydrocarbon such as toluene, xylene, and ethyl benzene; and alkyl aromatic groups each having a bonding site in the alkyl group portion of a polyalkyl aromatic hydrocarbon such as xylene and diethyl benzene. Of those, aliphatic groups having 2 to 4 carbon atoms are particularly preferable. In addition, multiple R⁴O's are identical to or different from one another.
It should be noted that p in the general formula (I) represents the number of the repeating and such a number that average value thereof is in the range of 0 to 10 or preferably 0 to 5.
In addition, R⁵ in the general formula (I) represents a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group herein specifically refers to: alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups; cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, various methyl cyclohexyl groups, various ethyl cyclohexyl groups, various propyl cyclohexyl groups, and various dimethyl cyclohexyl groups; aryl groups such as a phenyl group, various methyl phenyl groups, various ethyl phenyl groups, various dimethyl phenyl groups, various propyl phenyl groups, various trimethyl phenyl groups, various butyl phenyl groups, and various naphthyl groups; and aryl alkyl groups such as a benzyl group, various phenyl ethyl groups, various methyl benzyl groups, various phenyl propyl groups, and various phenyl butyl groups. Of those, a hydrocarbon group having 8 or less carbon atoms is preferable. When p represents 0, an alkyl group having 1 to 6 carbon atoms is preferable, and when p represents 1 or more, an alkyl group having 1 to 4 carbon atoms is particularly preferable.
The number of repeating units of formula (I) (that is, polymerization degree) may be appropriately selected according to a desired kinematic viscosity, which is typically 2 to 50 mm²/s (100°C), preferably 3 to 40 mm²/s (100°C).
The polyvinyl ether-based compound in the present invention can be produced by polymerization of the corresponding vinyl ether-based monomer. The vinyl ether-based monomer that can be used herein is represented by the following general formula (II),
where R¹, R², R³, R⁴, and R⁵, and p each have the same meaning as that described above. As the vinyl ether-based monomer, there are various compounds corresponding to the polyvinyl ether-based compound. Examples thereof include: vinyl methyl ether, vinyl ethyl ether, vinyl-n-propyl ether, vinyl-isopropyl ether, vinyl-n-butyl ether, vinyl-isobutyl ether, vinyl-sec-butyl ether, vinyl-tert-butyl ether, vinyl-n-pentyl ether, vinyl-n-hexyl ether, vinyl-2-methoxyethyl ether, vinyl-2-ethoxyethyl ether, vinyl-2-methoxy-1-methylethyl ether, vinyl-2-methoxy-propyl ether, vinyl-3,6-dioxaheptyl ether, vinyl-3,6,9-trioxadecyl ether, vinyl-1,4-dimethyl-3,6-dioxaheptyl ether, vinyl-1,4,7-trimethyl-3,6,9-trioxadecyl ether, vinyl-2,6-dioxa-4-heptyl ether, and vinyl-2,6,9-trioxa-4-decyl ether; 1-methoxypropene, 1-ethoxypropene, 1-n-propoxypropene, 1-isopropoxypropene, 1-n-butoxypropene, 1-isobutoxypropene, 1-sec-butoxypropene, 1-tert-butoxypropene, 2-methoxypropene, 2-ethoxypropene, 2-n-propoxypropene, 2-isopropoxypropene, 2-n-butoxypropene, 2-isobutoxypropene, 2-sec-butoxypropene, and 2-tert-butoxypropene; 1-methoxy-1-butene, 1-ethoxy-1-butene, 1-n-propoxy-1-butene, 1-isopropoxy-1-butene, 1-n-butoxy-1-butene, 1-isobutoxy-1-butene, 1-sec-butoxy-1-butene, 1-tert-butoxy-1-butene, 2-methoxy-1-butene, 2-ethoxy-1-butene, 2-n-propoxy-1-butene, 2-isopropoxy-1-butene, 2-n-butoxy-1-butene, 2-isobutoxy-1-butene, 2-sec-butoxy-1-butene, 2-tert-butoxy-1-butene, 2-methoxy-2-butene, 2-ethoxy-2-butene, 2-n-propoxy-2-butene, 2-isopropoxy-2-butene, 2-n-butoxy-2-butene, 2-isobutoxy-2-butene, 2-sec-butoxy-2-butene, and 2-tert-butoxy-2-butene. Those vinyl ether-based monomers can be produced by any known methods.
The terminals of the polyvinyl ether-based compound having the constitutional unit represented by the general formula (I) can be converted to a desired structure by a method in this application and a known method. As a converted group, a saturated hydrocarbon, an ether, an alcohol, a ketone, an amide, and a nitrile are exemplified.
As the polyvinyl ether-based compound used in the base oil in the refrigerator oil composition, a compound having the following terminal structure is suitable.
That is, the polyvinyl ether-based compound has:

(1) a structure in which one of the terminals is represented by the following general formula (III):

where R⁶, R⁷, and R⁸ each represent a hydrogen atom, or a hydrocarbon group having 1 to 8 carbon atoms and may be identical to or different from one another, R⁹ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, R¹⁰ represents a hydrocarbon group having 1 to 10 carbon atoms, q represents such a number that an average value thereof is 0 to 10, and in the case where multiple R⁹O's are present, multiple R⁹O's may be identical to or different from one another, and
the other terminal is represented by the following general formula (IV):
where R¹¹, R¹², and R¹³ each represent a hydrogen atom, or a hydrocarbon group having 1 to 8 carbon atoms and may be identical to or different from one another, R¹⁴ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, R¹⁵ represents a hydrocarbon group having 1 to 10 carbon atoms, r represents such a number that an average value thereof is 0 to 10, and when multiple R¹⁴O's are present, multiple R¹⁴O's may be identical to or different from one another;
(2) a structure in which one of the terminals is represented by the general formula (III) and the other terminal is represented by the following general formula (V):
where R¹⁶, R¹⁷, and R¹⁸ each represent a hydrogen atom, or a hydrocarbon group having 1 to 8 carbon atoms and may be identical to or different from one another, R¹⁹ and R²¹ each represent a divalent hydrocarbon group having 2 to 10 carbon atoms and may be identical to or different from each other, R²⁰ and R²² each represent a hydrocarbon group having 1 to 10 carbon atoms and may be identical to or different from each other, s and t each represent such a number that an average value thereof is 0 to 10 and my be identical to or different from each other, when multiple R¹⁹O's are present, multiple R¹⁹O's may be identical to or different from one another, and when multiple R²¹O' s are present, multiple R²¹O's may be identical to or different from one another;
(3) a structure in which one of the terminals is represented by the general formula (III) and the other terminal is a compound having an olefinic, unsaturated bond; or
(4) a structure in which one of the terminals is represented by the general formula (III) and the other terminal is represented by the following general formula (VI):
where R²³, R²⁴, and R²⁵ each represent a hydrogen atom, or a hydrocarbon group having 1 to 8 carbon atoms and may be identical to or different from one another.

The polyvinyl ether-based compound may be a mixture including two or more kinds of the polyvinyl ether-based compounds selected from those having the terminal structures in the items (1) to (4). As the mixture, for example, a mixture of the compounds in the items (1) and (4) and a mixture of the compounds in the items (2) and (3) are preferably exemplified.
The kinematic viscosity of the base oil at 100°C is preferably 2 to 50 mm²/s, more preferably 3 to 40 mm²/s, and still more preferably 4 to 30 mm²/s. When the kinematic viscosity is 2 mm²/s or more, favorable lubricity (load capacity resistance) is exhibited and sealing property is good, and when the kinematic viscosity is 50 mm²/s or less, energy saving is also favorable.
In addition, the molecular weight of the base oil is preferably 500 or more, more preferably 500 to 3,000, and still more preferably 600 to 2,500. The flashing point of the base oil is preferably 150°C or higher. When the molecular weight of the base oil is 500 or more, desirable performance as the refrigerator oil can be exhibited and the flashing point of the base oil can be set to 150°C or higher.
In the present invention, when the base oil has the above properties, the refrigerator oil composition may include, in addition to the polyvinyl ether derivative, another base oil at 50 mass% or less, preferably 30 mass% or less, and more preferably 10 mass% or less, and the refrigerator oil composition free of another base oil is still more preferred.
As the base oil that can be used together with the polyvinyl ether derivative, polyoxyalkylene glycols, or a copolymer of alkylene glycols or those monoethers and polyvinyl ethers, other polyesters, polyol ester-based compounds, polycarbonates, a hydrogenation product of α-olefin oligomer, a mineral oil, an alicyclic hydrocarbon compound, an alkylated aromatic hydrocarbon compound are exemplified.
Fluoropropene refrigerants are unstable because they have an olefin structure. In order to improve the stability of the refrigerant, the polyvinyl ether derivative contained in the refrigerator oil composition has a hydroxyl value of 17 mgKOH/g or less.

[Appropriate additive]

At least one kind of an additive selected from an extreme pressure agent, an oiliness agent, an antioxidant, an acid scavenger, a metal deactivator, and an anti-foaming agent can be incorporated into the refrigerator oil composition of the present invention.

(Extreme pressure agent)

Examples of the extreme pressure agent include phosphorus-based extreme pressure agents such as a phosphate, an acid phosphate, a phosphite, an acid phosphite, and amine salts thereof.
Of those phosphorus-based extreme pressure agents, tricresyl phosphate, trithiophenyl phosphate, tri(nonylphenyl) phosphite, dioleyl hydrogen phosphite, 2-ethylhexyldiphenyl phosphite, or the like is particularly preferable in terms of extreme pressure property, a frictional characteristic, and the like.
In addition, the examples of the extreme pressure agent include metal salts of carboxylic acids. The term "metal salts of carboxylic acids" as used herein preferably refers to metal salts of carboxylic acids each having 3 to 60 carbon atoms, and, further, aliphatic acids each having 3 to 30, and particularly preferably 12 to 30 carbon atoms. The examples further include metal salts of: dimer acids and trimer acids of the aliphatic acids; and dicarboxylic acids each having 3 to 30 carbon atoms. Of those, a metal salt of an aliphatic acid having 12 to 30 carbon atoms or of a dicarboxylic acid having 3 to 30 carbon atoms is particularly preferred.
On the other hand, a metal of which any such metal salt is constituted is preferably an alkali metal or an alkaline earth metal, and, in particular, is optimally an alkali metal.
Further, examples of the extreme pressure agents and extreme pressure agents other than those mentioned above include sulfur type extreme pressure agents such as sulfurized fat, sulfurized aliphatic acid, sulfurized ester, sulfurized olefin, dihydrocarvyl polysulphide, thiocarbamates, thioterpenes, and dialkyl thiodipropionates.
The blending amount of the above extreme pressure agent is in the range of preferably 0.001 to 5 mass% in ordinary cases, or particularly preferably 0.005 to 3 mass% with reference to the total amount of the composition in terms of lubricity and stability.
One kind of the extreme pressure agents may be used alone, or two or more kinds thereof may be used in combination.

(Oiliness agent)

Examples of the oiliness agents include, aliphatic saturated and unsaturated monocarboxylic acids such as stearic acid and oleic acid; polymerized aliphatic acids such as dimer acids and hydrogenated dimer acids; hydroxy aliphatic acids such as ricinoleic acid and 12-hydroxystearic acid; aliphatic saturated and unsaturated monohydric alcohols such as lauryl alcohol and oleyl alcohol; aliphatic saturated and unsaturated monoamines such as stearyl amine and oleylamine; aliphatic saturated and unsaturated monocarboxylic acid amides such as lauric acid amide and oleamide; and partial esters of a polyhydric alcohol such as glycerin and sorbitol, and an aliphatic saturated or unsaturated monocarboxylic acid.
One kind of the oiliness agent may be used alone, or two or more kinds thereof may be used in combination. In addition, the blending amount of the oiliness agent is selected from the range of typically 0.01 to 10 mass%, or preferably 0.1 to 5 mass% with reference to the total amount of the composition.

(Antioxidant)

A phenol-based antioxidant such as 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, or 2,2'-methylenebis(4-methyl-6-tert-butylphenol) or an amine-based antioxidant such as phenyl-α-naphthylamine or N.N'-di-phenyl-p-phenylenediamine is preferably blended as the antioxidant. The antioxidant is blended in the composition at a content of typically 0.01 to 5 mass%, or preferably 0.05 to 3 mass% in terms of an effect, economical efficiency, and the like.

(Acid scavenger)

Examples of the acid scavenger include: phenyl glycidyl ether; alkyl glycidyl ether; alkylene glycol glycidyl ether; cyclohexeneoxide; α-olefinoxide; and an epoxy compound such as epoxidized soybean oil. Of those, phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexeneoxide, or α-olefinoxide is preferable in terms of compatibility with the refrigerant.
Each of an alkyl group of the alkyl glycidyl ether and an alkylene group of the alkylene glycol glycidyl ether may be branched, and has typically 3 to 30, preferably 4 to 24, or particularly preferably 6 to 16 carbon atoms. In addition, one having a total of generally 4 to 50, preferably 4 to 24, or particularly preferably 6 to 16 carbon atoms is used as the α-olefinoxide. In the present invention, one kind of the acid scavenger may be used, or two or more kinds thereof may be used in combination. In addition, the blending amount of the acid scavenger is in the range of preferably 0.005 to 5 mass% in ordinary cases, or particularly preferably 0.05 to 3 mass% with reference to the composition in terms of an effect and the suppression of the generation of sludge.
In the present invention, the stability of the refrigerator oil composition can be improved by blending the acid scavenger. The combined use of the extreme pressure agent and the antioxidant with the acid scavenger exerts an additional improving effect on the stability.

(Metal deactivator and anti-foaming agent)

As the metal deactivator, for example, a copper deactivator such as N-[N,N'-dialkyl (alkyl group having 3 to 12 carbon atoms) aminomethyl]triazole is exemplified. As the antifoaming agent, for example, a silicone oil, a fluorinated silicone oil, and the like are exemplified.

[Method of lubricating refrigerator by using refrigerator oil composition]

The used amounts of the refrigerant and the refrigerator oil composition are such that the mass ratio of the refrigerant to the refrigerator oil composition is in the range of preferably 99/1 to 10/90, or more preferably 95/5 to 30/70. An amount of the refrigerant below the above range is not preferable because a reduction in refrigerating capacity of the refrigerator is observed. In addition, an amount of the refrigerant beyond the above range is not preferable because the lubricity of the composition reduces. The refrigerator oil composition of the present invention, which can be used in any one of various refrigerators, is particularly preferably applicable to the compression refrigerating cycle of a compression refrigerator.

(Refrigerator)

The refrigerator to which the refrigerant and refrigerator oil composition are applied has a refrigerating cycle which essentially contains a compressor, a condenser, an expansion mechanism (such as an expansion valve), and an evaporator, or contains a compressor, a condenser, an expansion mechanism, a drier, and an evaporator.
Here, the drier is preferably filled with a desiccant formed of zeolite having a pore diameter of 0.33 nm or less. In addition, as the zeolite, a natural zeolite or a synthetic zeolite may be exemplified. Zeolite having a CO₂ gas absorbing amount of 1.0% or less at 25°C and a CO₂ gas partial pressure of 33 kPa is more suitable. As the synthetic zeolite described above, XH-9 (trade name), XH-600 (trade name) manufactured by UNION SHOWA K.K., and the like are exemplified.
In the present invention, if the desiccant is used, moisture can be removed efficiently without absorbing of the refrigerant in the refrigerating cycle, and simultaneously, powderization of the desiccant due to deterioration of the desiccant itself is suppressed. Therefore, there is no possibility of clogging of pipes caused by the powderization or abnormal abrasion caused by entering of the powder into a sliding part of the compressor, whereby the refrigerator can be driven stably for a long time period.
Various sliding parts (such as a bearing) are present in a compressor in a refrigerator. In the present invention, a part composed of an engineering plastic, or a part having an organic or inorganic coating film is preferably used as each of the sliding parts in terms of, in particular, sealing property.
Preferable examples of the engineering plastic include a polyamide resin, a polyphenylene sulfide resin, and a polyacetal resin in terms of sealing property, sliding property, abrasion resistance, and the like.
In addition, examples of the organic coating film include a fluorine-containing organic resin coating film (such as a polytetrafluoroethylene coating film), a polyimide coating film and a polyamideimide coating film in terms of sealing property, sliding property, abrasion resistance, and the like. Further, examples thereof include a thermosetting insulating film formed using a resin coating material containing a crosslinking agent and a resin substrate formed of a polyhydroxyether resin and a polysulfone-based resin.
On the other hand, examples of the inorganic coating film include a graphite film, a diamond-like carbon film, a nickel film, a molybdenum film, a tin film, and a chromium film in terms of sealing property, sliding property, abrasion resistance, and the like. The inorganic coating film may be formed by a plating treatment, or may be formed by a physical vapor deposition method (PVD).
It should be noted that a part composed of, for example, a conventional alloy system such as an Fe base alloy, an Al base alloy, or a Cu base alloy can also be used as each of the sliding parts.

[System using refrigerator oil composition]

The refrigerator and refrigerator oil composition of the present invention can be used in each of a car air conditioner, an electrically-driven air conditioner, a gas heat pump, an air conditioner, a cold storage device, various hot water supply systems such as a vending machine or a showcase, and a refrigerating and heating system.
In the present invention, the water content in the system is preferably 300 mass ppm or less and more preferably 200 mass ppm or less. In addition, the residual air amount in the system is preferably 10 kPa or less and more preferably 5 kPa or less.
The refrigerator oil composition of the present invention includes a specific oxygen-containing compound as a base oil, has so low viscosity that energy saving can be improved, and has excellent sealing property.

Examples

Next, the present invention is described in more detail by way of examples. However, the present invention is by no means limited by those examples.
It should be noted that properties of the base oil and various characteristics of the refrigerator oil composition were determined according to the following procedure.

(1) Kinematic viscosity at 100°C

The kinematic viscosity at 100°C was measured according to JIS K2283-1983 by using a glass capillary viscometer.

(2) Hydroxyl value

The hydroxyl value was measured according to JIS K0070.

(3) Number average molecular weight

The number average molecular weight was measured by gel permeation chromatography (GPC).

(4) Flashing point

The flashing point was measured according to JIS K2265 (COC method)

(5) Two-layer separation temperature

A measuring tube for two-layer separation temperature (internal volume: 10 mL) was filled with water (0.6 g) and a refrigerant (2.4 g) and kept in a thermostatic chamber. The temperature in the thermostatic chamber was increased from room temperature (25°C) at a rate of 1°C/min, whereby a two-layer separation temperature was measured.

(6) Stability (sealed tube test)

A glass tube was filled with an oil (4 mL) and a refrigerant (HFC1234yf) (1 g) (water content of 200 ppm), and metal catalysts of iron, copper, and aluminum, and sealed. After the glass tube was kept at an air pressure of 26.6 kPa and at a temperature of 175°C for 30 days, oil appearance, catalyst appearance, and the presence or absence of sludge were visually observed and the acid value was measured.
The kinds of components used in preparation of the refrigerator oil composition are described below.
As the base oil, each of A1 to A7 and B1 to B7 was used. Table 1 shows the kind and the property of each base oil.

[Table 1]

Table 1

Kind of base oil	Hydroxyl value (mgKOH/g)	Kinematic viscosity at 100°C (mm²/s)	Number average molecular weight	Flashing point (°C)
A1	2	7.4	670	201
A2	3	10.2	840	210
A3	5	20.5	1,120	228
A4	9	10.3	830	211
A5	14	20.5	1,080	230
A6	19	10.4	740	203
A7	30	10.6	720	207
B1	3	9.8	870	205
B2	5	25.3	1,210	234
B3	7	11.2	860	213
B4	11	10.7	850	208
B5	15	7.2	645	198
B6	23	8.5	570	202
B7	34	6.7	480	182

[Note]
A1 to A7: a polyethyl vinyl ether (PEV) /polybutyl vinyl ether (PBV) copolymers (PEV/PBV molar ratio of 9/1) with different purification degrees in the synthesis
B1 to B7: Polyethyl vinyl ethers with different purification degrees in the synthesis

In addition, as the additives, the following C1 to C4 were used.

C1: Extreme pressure agent: tricresyl phosphate
C2: Acid scavenger: C14 α-olefin oxide
C3: Antioxidant: 2,6-di-t-butyl-4-methyl phenol
C4: Anti-foaming agent: silicon-based anti-foaming agent

Examples 1 to 10 and Comparative Examples 1 to 4

Refrigerator oil compositions having the compositions shown in Table 2 were prepared. HFC1234yf (2,3,3,3-tetrafluoropropene), was used as a refrigerant, and characteristics of the compositions were evaluated. Table 2 shows the results.

[Table 2]

Table 2-1

			Example
			1	2	3	4	5
Blending composition (mass%)	Base oil	Kind	A1	A2	A3	A4	A5
	Base oil	Content	Balance	Balance	Balance	Balance	Balance
	Extreme pressure agent	C1	1	1	1	1	1
	Acid scavenger	C2	1	1	1	1	1
	Antioxidant	C3	0.5	0.5	0.5	0.5	0.5
	Anti-foaming agent	C4	-	-	0.001	0.001	-
Two-layer separation temperature of HFC1234yf [Oil content of 20 mass%] (°C)			40<	40<	40<	40<	40<
Performance evaluation	Sealed tube test	Oil appearance	Good	Good	Good	Good	Good
		Catalyst appearance	Good	Good	Good	Good	Good
		Presence or absence of sludge	Absent	Absent	Absent	Absent	Absent
		Acid value (mgKOH/g)	0.01>	0.01>	0.01>	0.01>	0.02

[Table 3]

Table 2-2

			Example
			6	7	8	9	10
Blending composition (mass%)	Base oil	Kind	B1	B2	B3	B4	B5
	Base oil	Content	Balance	Balance	Balance	Balance	Balance
	Extreme pressure agent	C1	1	1	1	1	1
	Acid scavenger	C2	1	1	1	1	1
	Antioxidant	C3	0.5	0.5	0.5	0.5	0.5
	Anti-foaming agent	C4	-	-	-	-	-
Two-layer separation temperature of HFC1234yf [Oil content of 20 mass%] (°C)			40<	40<	40<	40<	40<
Performance evaluation	Sealed tube test	Oil appearance	Good	Good	Good	Good	Good
		Catalyst appearance	Good	Good	Good	Good	Good
		Presence or absence of sludge	Absent	Absent	Absent	Absent	Absent
		Acid value (mgKOH/g)	0.01>	0.01>	0.01>	0.03	0.04

[Table 4]

Table 2-3

			Comparative Example
			1	2	3	4
Blending composition (mass%)	Base oil	Kind	A6	A7	B8	B7
	Base oil	Content	Balance	Balance	Balance	Balance
	Extreme pressure agent	C1	1	1	1	1
	Acid scavenger	C2	1	1	1	1
	Antioxidant	C3	0.5	0.5	0.5	0.5
	Anti-foaming agent	C4	-	-	-	-
Two-layer separation temperature of HFC1234yf [Oil content of 20 mass%] (°C)			40<	40<	40<	40<
Performance evaluation	Sealed tube test	Oil appearance	Yellow	Yellowish brown	Yellow	Yellowish brown
		Catalyst appearance	Slight color change by Cu	Slight color change by Cu	Slight color change by Cu	Slight color change by Cu
		Presence or absence of sludge	Slight	Slight	Slight	Slight
		Acid value (mgKOH/g)	0.8	1.5	1.2	1.8

From Table 2, the following are revealed.
Anyone of the refrigerator oil compositions of the present invention (Examples 1 to 10) has a two-layer separation temperature exceeding 40°C, has favorable oil appearance and catalyst appearance, and an extremely low acid value of 0.04 mgKOH/g or less.
On the contrary, while any one of the refrigerator oil compositions in Comparative Examples 1 to 4 using the polyvinyl ether derivative having a hydroxyl value exceeding 17 mgKOH/g as a base oil has a two-layer separation temperature exceeding 40°C, in the sealed tube test, the oil appearance is yellow or yellowish brown, there are a slight color change in the catalyst appearance by Cu and a slight generation of sludge, and the acid value is as high as 0.8 to 1.8 mgKOH/g.

[Industrial Applicability]

The present invention uses a refrigerant having a specific structure, having a low global warming potential and being applicable to, in particular, current car air conditioner systems or the like. The lubricating oil composition used with the refrigerant has excellent stability as well as excellent compatibility with the refrigerant. No generation of sludge is confirmed in a sealed tube test when the lubricating oil composition is used.

Claims

Use of the following refrigerant (i) and lubricating oil composition (ii) in a refrigerator:
(i) a refrigerant including:
- at least one fluorinated propene, and

- optionally up to 30 mass%, based on the total mass of the refrigerant, of one or more saturated fluorinated hydrocarbon compounds; and

(ii) a lubricating oil composition comprising a base oil which consists of at least one polyvinyl ether derivative having a hydroxyl value of 17 mgKOH/g or less.
Use according to Claim 1, wherein each fluorinated propene is selected from pentafluoropropenes, 2,3,3,3-tetrafluoropropene and 3,3,3-trifluoropropene.
Use according to Claim 1, wherein each saturated fluorinated hydrocarbon compound is a saturated fluorinated C_1-3 hydrocarbon.
Use according to Claim 1, wherein the base oil has a kinematic viscosity of 2-50 mm²/s at 100°C.
Use according to Claim 1, wherein the base oil has a molecular weight of 500 or more.
Use according to Claim 1, wherein the at least one polyvinyl ether derivative contains, as a main component, a polyvinyl-based compound having a constituent unit represented by the following formula (I):
wherein:
R¹-R³ each independently represent H or a C_1-8 hydrocarbon group;

R⁴ is a divalent C_2-10 hydrocarbon group;

R⁵ is a C_1-10 hydrocarbon group; and

p is the average number of repeating units and is in the range of 0-10.
Use according to Claim 1, wherein the lubricating oil composition further comprises at least one kind of additive selected from an extreme pressure agent, an oiliness agent, an antioxidant, an acid scavenger, a metal deactivator, and an anti-foaming agent.
Use according to Claim 7, wherein the refrigerator comprises a sliding part which is formed of an engineering plastic or which includes an organic or inorganic coating film.
Use according to Claim 8, wherein the organic coating film is a polytetrafluoroethylene coating film, a polyimide coating film, a polyamideimide coating film, or a thermosetting insulating film formed using a resin coating material containing a crosslinking agent and a resin substrate formed of a polyhydroxyether resin and a polysulfone-based resin.
Use according to Claim 8, wherein the inorganic coating film is a graphite film, a diamond-like carbon film, a tin film, a chromium film, a nickel film or a molybdenum film.
Use of a refrigerant and a lubricating oil composition as defined in Claim 1 in an air conditioner, preferably a car air conditioner or an electrically-driven air conditioner; a gas heat pump; a cold storage device; a hot-water supply system for a vending machine or a showcase; or a refrigerating and heating system.
Use according to Claim 11, wherein the water content of the system is 300 mass ppm or less, and the residual air content of the system is 10 kPa or less.